DK173486B1 - Process for producing small, zeotypic crystals - Google Patents
Process for producing small, zeotypic crystals Download PDFInfo
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- DK173486B1 DK173486B1 DK199801505A DKPA199801505A DK173486B1 DK 173486 B1 DK173486 B1 DK 173486B1 DK 199801505 A DK199801505 A DK 199801505A DK PA199801505 A DKPA199801505 A DK PA199801505A DK 173486 B1 DK173486 B1 DK 173486B1
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
4 DK 173486 B14 DK 173486 B1
Denne opfindelse angår fremstilling og isolering af små, zeotype krystaller.This invention relates to the production and isolation of small, zeotypic crystals.
Især angår opfindelsen en særlig fremgangsmåde, ved hvilken det er muligt at opnå veldefinerede stør-5 reiser for zeotype krystaller, der for eksempel er nyttige ved fremstilling af katalysatorer.In particular, the invention relates to a particular method by which it is possible to obtain well-defined sizes for zeotype crystals which are useful, for example, in the preparation of catalysts.
Zeotype er defineret som et fællesnavn for zeolitter og beslægtede forbindelser, i hvilke Si helt eller delvis er substitueret med Al og/eller P og/eller me-10 taller. Zeolitter er zeotyper med en lav grad af substitution af Si.Zeotype is defined as a common name for zeolites and related compounds in which Si is fully or partially substituted with Al and / or P and / or metals. Zeolites are zeotypes with a low degree of substitution of Si.
Små zeotype krystaller har interesse i forbindelse med en række katalytiske reaktioner, og der findes rapporter over mange forsøg på at minimisere krystalstør-15 reisen.Small zeotype crystals are of interest in a number of catalytic reactions, and there are reports of many attempts to minimize the crystal size-15 journey.
Castagnola et al. benytter lavtemperaturældning i nærvær af saccharose til syntese af 250 nm aggregater af enkelte 13 nm krystaller af zeolit X (N.B. Castagnola, P.K. Dutta, J. Phys. Chem. B, 1998, 102, 1696-20 1702). Under formindskelse af Si/Al-forholdet og forøgelse af OH/Si-forholdet syntetiserer Yamamura et al.Castagnola et al. utilizes low temperature aging in the presence of sucrose to synthesize 250 nm aggregates of single 13 nm crystals of zeolite X (N.B. Castagnola, P. K. Dutta, J. Phys. Chem. B, 1998, 102, 1696-20 1702). While decreasing the Si / Al ratio and increasing the OH / Si ratio, Yamamura et al.
30-50 nm ZSM-5 bestående af enkelte 13-20 nm krystaller (M. Yamamura, K. Chaki, T. Wakatsuki, H. Okado, K. Fu-jimoto. Zeolites, 1994, 14, 643-649).30-50 nm ZSM-5 consisting of single 13-20 nm crystals (M. Yamamura, K. Chaki, T. Wakatsuki, H. Okado, K. Fu-jimoto. Zeolites, 1994, 14, 643-649).
25 Zeolit Beta blev syntetiseret med en krystalstør relse ned til 10 nm ved formindskelse af Si/Al-forhol-det i fravær af alkalimetalkationer, som beskrevet af M.A. Camblor, A. Corma, A. Mifsud, J. Pérez-Pariente og S. Valencia, Progress in Zeolite and Microporous Mate-30 rials, Studies in Surface Science and Catalysis, 1997, 105, 341-348.Zeolite Beta was synthesized with a crystal size down to 10 nm by reducing the Si / Al ratio in the absence of alkali metal cations, as described by M.A. Camblor, A. Corma, A. Mifsud, J. Pérez-Pariente, and S. Valencia, Progress in Zeolite and Microporous Mate rials, Studies in Surface Science and Catalysis, 1997, 105, 341-348.
Under variationer af forholdene mellem Si/Al,Under variations of the Si / Al ratio,
HjO/Al og K/Al fremstiller Meng og medarbejdere 30 nm krystaller af zeolit L [X. Meng, Y. Zhang, W. Pang, The i. y.HjO / Al and K / Al make Meng and co-workers 30 nm crystals of zeolite L [X. Meng, Y. Zhang, W. Pang, The i. Y.
35 Proceedings of the 9C International Zeolite confe- 2 DK 173486 B1 rence, Montreal 1992, Eds. R. von Ballmoos et al., 297-304] .35 Proceedings of the 9C International Zeolite Confederation, Montreal 1992, Eds. R. von Ballmoos et al., 297-304].
Fordelene ved små størrelser for zeotype krystaller er især, 5 (1) en reduktion af diffusionsmodstanden i zeotypen (K. Beschmann, L. Riekert, J. Catal. , 1993, 141, 548-565), (N.Y. Chen, W.E. Garwood, J. Catal., 1978, 52, 453-458), (S.B. Pu, T. Inui, Zeolites, 1996, 17, 334- 33 9) ; 10 (2) en reduktion af deaktiveringshastigheden for zeoty-pen forårsaget af afsætning af koks på den ydre overflade (M. Yamamura, K. Chaki, T. Wakatsuki, H. Okado, K. Fujimoto, Zeolites, 1994, 14, 643-649), (I.E. Maxwell, W.H.J. Stork, Stud. Surf. Sci. Catal., 58, 1991, 15 571-630) .The advantages of small sizes for zeotype crystals are, in particular, 5 (1) a reduction of the diffusion resistance in the zeotype (K. Beschmann, L. Riekert, J. Catal., 1993, 141, 548-565), (NY Chen, WE Garwood, J. Catal., 1978, 52, 453-458), (SB Pu, T. Inui, Zeolites, 1996, 17, 334- 33 9); (2) a reduction in the deactivation rate of the zeotype caused by coke deposition on the outer surface (M. Yamamura, K. Chaki, T. Wakatsuki, H. Okado, K. Fujimoto, Zeolites, 1994, 14, 643- 649), (IE Maxwell, WHJ Stork, Stud. Surf. Sci. Catal. 58, 1991, 571-630).
Det er nu blevet fundet, at størrelsen for de zeotype krystaller kan kontrolleres ved krystallisation af zeotypen inden i et porøst bæremateriale med porer, der er mindre end 100 nm. Det er foretrukket muligt at 20 fjerne det porøse bæremateriale til isolation af den rene zeotype, eller den er nyttig som en komponent af en ønsket katalysator. Eksempler på typiske porøse bærematerialer er carbon og magnesiumoxid, der repræsenterer gruppen af fjernelige porøse bærematerialer, og 25 siliciumoxid-aluminiumoxid, der kan være en ønsket bestanddel af en katalysator. Men alle mulige andre egnede materialer med porer, der er mindre end 100 nm, kan benyttes som bærematerialer.It has now been found that the size of the zeotype crystals can be controlled by crystallizing the zeotype within a porous support having pores less than 100 nm. It is preferably possible to remove the porous support material for isolation of the pure zeotype, or it is useful as a component of a desired catalyst. Examples of typical porous carriers are carbon and magnesium oxide representing the group of removable porous carriers, and silica-alumina which may be a desired component of a catalyst. However, all possible other suitable materials with pores less than 100 nm can be used as carrier materials.
De parametre, der kontrollerer størrelser for zeo-30 type krystaller, er porestørrelsen for det porøse bæremateriale, koncentrationen af precursorer for zeotypen i porerne i det porøse bæremateriale og de detaljerede krystallisationsbetingelser.The parameters controlling the sizes of zeo-type crystals are the pore size of the porous support, the concentration of precursors of the zeotype in the pores of the porous support, and the detailed crystallization conditions.
Porestørrelsesfordelinger i porøse bærematerialer 35 kan bestemmes ved hjælp af BET metoden og ved Hg-ind- 3 DK 173486 B1 trængning. Krystalstørrelser for zeotyper kan ved hjælp af Debye-Scherrer metoden bestemmes ud fra tilvæksten i bredde for røntgen-pulverdiffraktionslinier (XRPD) og ved hjælp af transmissions-elektronmikroskopi (TEM).Pore size distributions in porous substrates 35 can be determined by the BET method and by Hg penetration. Crystal sizes for zeotypes can be determined using the Debye-Scherrer method based on the x-ray powder diffraction (XRPD) gain in width and by transmission electron microscopy (TEM).
5 I overenstemmelse med det ovennævnte fund tilveje bringer denne opfindelse en særlig fremgangsmåde til fremstilling af små zeotype krystaller med kontrolleret størrelse. Fremgangsmåden er ejendommelig ved at omfatte følgende trin 10 inden i et porøst materiale, i hvilket hovedande len af porerne er mindre end 100 nm, at syntetisere en syntetisk gel, der i det væsentlige består af (a) en zeotype precursorsammensætning omfattende hydrat iserede oxider af Si, Al og P og metalforbindelser, 15 (b) en zeolit-skabelon; at opvarme eller autoklavere det porøse bæremateriale indeholdende syntetisk gel til dannelse af zeotype krystaller; at vaske og tørre det porøse bæremateriale inde-20 holdende zeotype krystaller; og eventuelt at fjerne det porøse bæremateriale og isolere de zeotype krystaller.In accordance with the aforementioned finding, this invention provides a particular method for producing small size controlled zeotype crystals. The method is characterized by comprising the following step 10 within a porous material, in which the major proportion of the pores is less than 100 nm, to synthesize a synthetic gel consisting essentially of (a) a zeotype precursor composition comprising hydrated isitic oxides of Si, Al and P and metal compounds, (b) a zeolite template; heating or autoclaving the porous support material containing synthetic gel to form zeotype crystals; washing and drying the porous support containing zeotype crystals; and optionally removing the porous support material and isolating the zeotypic crystals.
En fordel ved opfindelsen er, at den maksimale størrelse for de opnåede zeotype krystaller kan kon-25 trolieres, idet den aldrig kan overskride porediameteren i det porøse bæremateriale.An advantage of the invention is that the maximum size of the obtained zeotype crystals can be controlled as it can never exceed the pore diameter of the porous support material.
En yderligere fordel ved fremgangsmåden ifølge denne opfindelse er, at den kan benyttes til fremstilling af alle mulige typer af zeotyper.A further advantage of the method of this invention is that it can be used to produce all possible types of zeotypes.
30 Endnu en fordel er, at graden af agglomeration mellem de enkelte zeotype krystaller reduceres kraftigt, når krystallisationen skrider frem inden i det porøse bæremateriale. Dette er nyttigt ved anvendelser, hvor det porøse bæremateriale ikke fjernes fra zeoty-35 pen, idet zeotypen af denne grund er fordelt på for- 4 DK 173486 B1 træffelig måde i hele poresystemet i det porøse bæremateriale .Yet another advantage is that the degree of agglomeration between the individual zeotype crystals is greatly reduced as the crystallization progresses within the porous support material. This is useful in applications where the porous support is not removed from the zeotype, for this reason the zeotype is distributed in a convenient manner throughout the porous system of the porous support.
Endnu en yderligere fordel, når der benyttes fjer-nelige bærematerialer såsom carbon eller MgO, der fjer-5 nes ved henholdsvis pyrolyse og sur hydrolyse, er at fjernelsen af det porøse bæremateriale sikrer et sekundært poresystem ind mellem de zeotype krystaller, hvilket letter diffusion af reaktanter ind i zeotypen og af reaktionsprodukter ud af de resulterende zeotype 10 katalysatorer.Yet another advantage when using removable support materials such as carbon or MgO removed by pyrolysis and acid hydrolysis, respectively, is that the removal of the porous support ensures a secondary pore system between the zeotypic crystals, which facilitates diffusion of reactants into the zeotype and of reaction products out of the resulting zeotype 10 catalysts.
Eksempler på specifikke udførelsesformer for denne opfindelse er givet nedenfor.Examples of specific embodiments of this invention are given below.
15 DETALJERET BESKRIVELSE AF OPFINDELSENDETAILED DESCRIPTION OF THE INVENTION
I alle de nedenfor anførte Eksempler benyttedes destilleret vand som kilde for vand. Derudover er alle de nedenfor anførte sammensætninger for syntesegeler 20 anført som molforhold for de enkelte komponenter.In all of the Examples below, distilled water was used as the source of water. In addition, all of the synthesis gel 20 compositions listed below are listed as mole ratios for the individual components.
Alment fremstilles zeotyper under anvendelse af en primær Si/Al/P-kilde (precursorkilde) , der hydrolyseres under syntesebetingelserne, og en skabelonblanding, der i afhængighed af den zeotype, der skal fremstilles, in-25 deholder en organisk eller uorganisk (alkali) skabelon, der fremmer dannelse af den ønskede zeotype ud fra den hertil svarende syntesegel (hydrolyseret precursorkilde samt skabelonblanding). Skabelonblandingen kan ud over zeotype-promotorer (skabelonen) indeholde forbindelser, 30 der tilvejebringer ønskede grundstoffer i den resulterende zeotype (sekundære precursorkilder), men som er uopløselige i den primære precursorkilde og derfor tilsættes sammen med skabelonen i skabelonblandingen. Den opnåede syntesegel kan indeholde hydrolyserede oxidfor-35 bindeiser af Si, Al, P og metaller samt skabelonen.Generally, zeotypes are prepared using a primary Si / Al / P source (precursor source) which is hydrolyzed under the synthesis conditions and a template mixture which, depending on the zeotype to be prepared, contains an organic or inorganic (alkali) template which promotes formation of the desired zeotype from the corresponding synthesis gel (hydrolyzed precursor source and template mixture). The template blend may contain, in addition to zeotype promoters (the template), compounds which provide desired elements in the resulting zeotype (secondary precursor sources) but which are insoluble in the primary precursor source and are therefore added together with the template in the template mixture. The synthesis gel obtained can contain hydrolyzed oxide junctions of Si, Al, P and metals as well as the template.
5 DK 173486 B15 DK 173486 B1
Zeotype krystaller opnås fra syntesegelen ved opvarmning eller autoklavering af syntesegelen ifølge kendt teknik. Organiske (flygtige) skabeloner fjernes fra den opnåede zeotype under aktiveringen.Zeotype crystals are obtained from the synthesis gel by heating or autoclaving the synthesis gel of the prior art. Organic (volatile) templates are removed from the obtained zeotype during activation.
5 De ved syntesen benyttede kemiske kilder skal en ten være opløselige i vand eller et flygtigt, organisk opløsningsmiddel. Nedenfor gives eksempler på typiske kilder for Si, Al og P, men en hvilken som helst kilde, der opfylder opløselighedskravet, kan benyttes.5 The chemical sources used in the synthesis must be soluble in water or a volatile organic solvent. Examples of typical sources for Si, Al and P are given below, but any source that meets the solubility requirement can be used.
10 Typiske kilder for silicium er MjSiO^, M = Na, KTypical sources of silicon are MjSiO4, M = Na, K
eller Si(OR)4, R = alkyl.or Si (OR) 4, R = alkyl.
Typiske kilder for aluminium er Al(N03)3, A12(S04)3, NaAl02, KAlOz og Al(OR)4, R * alkyl.Typical sources of aluminum are Al (NO3) 3, A12 (SO4) 3, NaAlO2, KAlOz and Al (OR) 4, R * alkyl.
Typiske kilder for phosphor er Η3ΡΟχ, x » 2, 3, 4.Typical sources of phosphorus are Η3ΡΟχ, x »2, 3, 4.
15 Typiske organiske skabeloner er alkylaminer eller tetraalkylammoniumsalte samt tetraalkylammoniumbromider eller -hydroxider.Typical organic templates are alkylamines or tetraalkylammonium salts and tetraalkylammonium bromides or hydroxides.
Typiske uorganiske skabeloner er alkalimetaller.Typical inorganic templates are alkali metals.
20 Eksempel 1:Example 1:
Krystallisation af ZSM-5Crystallization of ZSM-5
Et referenceeksempel blev foretaget på følgende måde. Man benyttede tetraethylorthosilicat (TEOS) og aluminiumisopropoxid (Al(Oi-Pr)3) som kilder for sili-25 ciumoxid og aluminiumoxid og benyttede tetrapropylammo-niumhydroxid (TPAOH) som skabelon. Synteseblandingen er baseret på syntesen af ZSM-5 beskrevet i (A.E. Persson, B.J. Schoeman, J. Sterte, J. Ottersted, Zeolites, 1994, 14, 557-567) og (M. Ghamami, L.B. Sand, Zeolites, 1983, 30 3, 155-162) med nogle få modifikationer.A reference example was made as follows. Tetraethyl orthosilicate (TEOS) and aluminum isopropoxide (Al (Oi-Pr) 3) were used as sources of silica and alumina, and tetrapropylammonium hydroxide (TPAOH) was used as template. The synthesis mixture is based on the synthesis of ZSM-5 described in (AE Persson, BJ Schoeman, J. Sterte, J. Ottersted, Zeolites, 1994, 14, 557-567) and (M. Ghamami, LB Sand, Zeolites, 1983, 30 3, 155-162) with a few modifications.
Man opløste 6,58 g Al(Oi-Pr)3 i en blanding af 0,200 kg TPAOH (40%, Aldrich), 0,044 kg ammoniak (25%, riedel-de Haén) og 0,220 kg vand. Under omrøring satte man 0,340 kg TEOS (98%, Aldrich) til blandingen og æl-35 dede opløsningen i 3 timer.6.58 g of Al (Oi-Pr) 3 was dissolved in a mixture of 0.200 kg of TPAOH (40%, Aldrich), 0.044 kg of ammonia (25%, Riedel-de Haén) and 0.220 kg of water. With stirring, 0.340 kg of TEOS (98%, Aldrich) was added to the mixture and the solution was heated for 3 hours.
6 DK 173486 B16 DK 173486 B1
Der opnåedes en syntesegel i bæreren med følgende sammensætning: 25 Si02 : 6 TPAOH : 10 NH3 : 200 H20 : 100 EtOH 5A synthesis gel was obtained in the carrier of the following composition: 25 SiO 2: 6 TPAOH: 10 NH 3: 200 H 2 O: 100 EtOH 5
Syntesegelen blev overført til et porcelænsbæger, der blev anbragt i en autoklav, der indeholdt tilstrækkeligt vand til produktion af mættet vanddamp.The synthesis gel was transferred to a porcelain beaker placed in an autoclave containing sufficient water to produce saturated water vapor.
Produktet blev vasket med vand, indtil pH-værdien 10 for vaskevandet nåede 7-8.The product was washed with water until the pH of the wash water reached 7-8.
Faseidentifikationen (XRPD) blev udført på et Philips PW 1820 Diffractometer under anvendelse af monokromatisk CuKor-stråling (40 kV og 40 mA) . For den syntetiserede ZSM-5 viste en sådan XRPD tilstedeværelse af 15 krystallinsk ZSM-5 med en krystalstørrelse på mere end 100 nm.The phase identification (XRPD) was performed on a Philips PW 1820 Diffractometer using monochromatic CuKor radiation (40 kV and 40 mA). For the synthesized ZSM-5, such an XRPD showed the presence of 15 crystalline ZSM-5 with a crystal size greater than 100 nm.
Eksempel 2:Example 2:
Krystallisation af ZSM-5 i carbon 20 Carbonsort (Black Pearls® BP-700 og Black Pearls® BP-2000, Cabot Corp.) blev benyttet som bæremateriale.Crystallization of ZSM-5 in carbon 20 Carbon black (Black Pearls® BP-700 and Black Pearls® BP-2000, Cabot Corp.) was used as the carrier material.
Disse materialer har mesoporer med en snæver porestørrelsesfordeling og et tilstrækkelig højt porevolumen.These materials have mesopores with a narrow pore size distribution and a sufficiently high pore volume.
To forskellige metoder blev benyttet ved fremstil-25 lingen af zeolitter i poresystemet i bæreren. Ved det ene forsøg hydrolyseredes siliciumoxidkilden til siliciumoxid under basiske betingelser før imprægnering med skabelonen, og ved det andet forsøg hydrolyseredes siliciumoxidkilden med præ-imprægneret skabelon. Ved alle 30 imprægneringstrin benyttedes imprægnering ved begyndel-sesfugtighed for at undgå krystallisation uden for poresystemet .Two different methods were used in the preparation of zeolites in the pore system of the support. In one experiment, the silica source was hydrolyzed to silica under basic conditions prior to impregnation with the template, and in the second experiment, the silica source was hydrolyzed with pre-impregnated template. At all 30 impregnation stages, initial moisture was used to avoid crystallization outside the pore system.
35 7 DK 173486 B135 7 DK 173486 B1
Eksempel 2.λ:Example 2.λ:
Præhydrolyse af kilden for silicium, uden aluminiumPre-hydrolysis of the source of silicon, without aluminum
Som et eksempel tørredes 1,00 kg BP-700 med et Hg-porevolumen på 0,728 1/kg og en BET-poreradius på 10,6 5 nm 3 timer i en ovn ved 150°C.As an example, 1.00 kg BP-700 was dried with a Hg pore volume of 0.728 L / kg and a BET pore radius of 10.6 5 nm 3 hours in an oven at 150 ° C.
En syntesegel i bæreren med følgende sammensætning:A synthesis gel in the carrier having the following composition:
25 Si02 : 5,2 TPAOH : 10 NH3 : 149 H20 : 23 EtOHSiO 2: 5.2 TPAOH: 10 NH 3: 149 H2 O: 23 EtOH
10 blev opnået som nedenfor beskrevet.10 were obtained as described below.
En opløsning af 0,34 kg TEOS (98%, Aldrich) og 0,2 9 kg ethanol (> 95%, Bie & Berntsen A/S) blev imprægneret i bæreren, bæreren blev tørret i 5 timer ved 15 stuetemperatur, imprægneret med en blanding af 0,11 kg ammoniak (25%, Riedel-de Haén), 0,03 kg vand og 0,046 kg ethanol (> 95%, Bie & Berntsen A/S) og tørret ved stuetemperatur i 12 timer fulgt af ved 120°C i 2¾ time.A solution of 0.34 kg TEOS (98%, Aldrich) and 0.2 9 kg ethanol (> 95%, Bie & Berntsen A / S) was impregnated in the carrier, the carrier was dried for 5 hours at room temperature, impregnated with a mixture of 0.11 kg of ammonia (25%, Riedel-de Haén), 0.03 kg of water and 0.046 kg of ethanol (> 95%, Bie & Berntsen A / S) and dried at room temperature for 12 hours followed by 120 ° C for 2¾ hours.
En skabelonblanding blev fremstillet ved blanding 20 af 0,17 kg tetrapropyammoniumhydroxid (40%, Aldrich) med 0,04 kg vand fulgt af tilsætning af 0,045 kg ammoniak (25%, Riedel-de Haén) og 0,07 kg ethanol (> 95%,A template mixture was prepared by mixing 20 of 0.17 kg of tetrapropyammonium hydroxide (40%, Aldrich) with 0.04 kg of water followed by the addition of 0.045 kg of ammonia (25%, Riedel-de Haén) and 0.07 kg of ethanol (> 95 %,
Bie & Berntsen A/S).Bie & Berntsen A / S).
Skabelonblandingen blev imprægneret i bæreren og 25 ældet ved stuetemperatur i 3 timer i et forseglet vandbad. Efter ældningen blev den imprægnerede bærer overført til en porcelænsskål og anbragt i en rustfri stålautoklav indeholdende vand. Den imprægnerede bærer blev derefter hydrotermisk autoklaveret ved 180eC i 48 timer 30 under statiske betingelser.The template mixture was impregnated in the support and aged at room temperature for 3 hours in a sealed water bath. After aging, the impregnated support was transferred to a porcelain bowl and placed in a stainless steel autoclave containing water. The impregnated support was then hydrothermally autoclaved at 180 ° C for 48 hours under static conditions.
Autoklaven blev afkølet til stuetemperatur, og produktet blev suspenderet i vand, isoleret ved suge-filtrering, igen suspenderet i vand og filtreret igen. Vasketrinnet blev gentaget fire gange fulgt af et 35 vasketrin med ethanol. Produktet blev tørret ved 110eCThe autoclave was cooled to room temperature and the product was suspended in water, isolated by suction filtration, resuspended in water and filtered again. The washing step was repeated four times followed by a washing step with ethanol. The product was dried at 110 ° C
8 DK 173486 B1 i 3 timer, før man udførte analyse ved røntgen-pulverdiffraktion (XRPD).8 DK 173486 B1 for 3 hours before performing analysis by X-ray powder diffraction (XRPD).
Eksempel 2.B: 5 Præhydrolyse af kilden for silicium, med aluminiumExample 2.B: 5 Prehydrolysis of the source of silicon, with aluminum
Eksempel 2.A blev gentaget, idet skabelonblandingen dog nu blev fremstillet ved opløsning af 6, S g aluminiumpropoxid (98%, Struers) i en opløsning af 0,17 kg tetrapropylammoniumhydroxid (40%, Aldrich) og 0,04 10 kg vand fulgt af tilsætning af 0,045 kg ammoniak (25%,Example 2.A was repeated, however, the template mixture was now prepared by dissolving 6.7 g of aluminum propoxide (98%, Struers) in a solution of 0.17 kg of tetrapropylammonium hydroxide (40%, Aldrich) and 0.04 10 kg of water followed. of the addition of 0.045 kg of ammonia (25%,
Riedel-de Haén) og 0,07 kg ethanol (> 95%, Bie & Bernt-sen A/S).Riedel-de Haén) and 0.07 kg of ethanol (> 95%, Bie & Bernt-sen A / S).
Derefter opnåedes en syntesegel i bæreren med følgende sammensætning: 15 25 Si02 : 0,25 Al2C>3 : 5,2 TPAOH : 10 NH-j : 149 H20 :Then a synthesis gel was obtained in the carrier of the following composition: SiO₂: 0.25 Al₂C> 3: 5.2 TPAOH: NH NH j: 149H₂O:
23 EtOHEtOH
Der benyttedes samme procedurer som i Eksempel 1 20 i trinnét med hydrotermal autoklavering og vasketrinnet .The same procedures as in Example 1 20 were used in the hydrothermal autoclaving step and the washing step.
Eksempel 2.C:Example 2.C:
Præimprægnering af skabelon 25 Der benyttedes en procedure svarende til Eksempel 2.B, men nu blev imprægneringen af skabelonen foretaget før imprægneringen af kilden for siliciumoxid.Pre-impregnation of template 25 A procedure similar to Example 2.B was used, but now the impregnation of the template was done prior to impregnation of the source of silica.
Skabelonblandingen blev fremstillet ved at blande 0,19 kg tetrapropylammoniumhydroxid (40%, Aldrich) med 30 0, 11 kg vand fulgt af tilsætning af 0,04 kg ammoniak (25%, Riedel-de Haén) og 0,29 kg ethanol (> 95%, Bie & Berntsen A/S).The template mixture was prepared by mixing 0.19 kg of tetrapropylammonium hydroxide (40%, Aldrich) with 30.0, 11 kg of water followed by the addition of 0.04 kg of ammonia (25%, Riedel-de Haén) and 0.29 kg of ethanol (> 95%, Bie & Berntsen A / S).
Opløsningen blev imprægneret i bæreren og tørret i 3 timer ved stuetemperatur.The solution was impregnated in the carrier and dried for 3 hours at room temperature.
35 9 DK 173486 B135 9 DK 173486 B1
Efter tørring blev bæreren imprægneret med 0,34 kg TEOS og ældet i et forseglet vandbad i 3 timer.After drying, the support was impregnated with 0.34 kg TEOS and aged in a sealed water bath for 3 hours.
Der opnåedes en syntesegel i bæreren med følgende sammensætning: 5A synthesis gel was obtained in the carrier of the following composition: 5
25 Si02 : 5,8 TPAOH : 9 NH^ : 220 H20 : 100 EtOHSiO 2: 5.8 TPAOH: 9 NH 2: 220 H2 O: 100 EtOH
Der benyttedes samme procedurer som i Eksempel 1 i trinnet med hydrotermal autoklavering og vasketrin-10 net.The same procedures were used as in Example 1 in the hydrothermal autoclaving step and the washing step.
Eksempel 2.D:Example 2.D:
Præimprægnering af skabelon og aluminiumPreprinting of template and aluminum
Eksempel 2.C blev gentaget, men nu blev 6,6 g alu-15 miniumisopropoxid opløst i skabelonblandingen.Example 2.C was repeated, but now 6.6 g of aluminum isopropoxide was dissolved in the template mixture.
Der opnåedes en syntesegel i bæreren med følgende sammensætning: 25 Si02 : 0,25 A1203 : 5,8 TPAOH : 9 NHj : 220 H20 :A synthesis gel was obtained in the carrier of the following composition: 25 SiO 2: 0.25 Al 2 O 3: 5.8 TPAOH: 9 NH 2: 220 H 2 O:
20 100 EtOH100 EtOH
Der benyttedes samme procedurer som i Eksempel 2.C ved tørring, imprægnering af siliciumoxidkilde, trinnet med hydrotermal autoklavering og vasketrinnet.The same procedures as in Example 2.C were used for drying, impregnating the silica source, the hydrothermal autoclaving step and the washing step.
2525
Eksempel 2.E:Example 2.E:
Krystallisation af ZSM-5 i storporet carbonCrystallization of ZSM-5 in Large Pore Carbon
Der benyttedes en synteseprocedure svarende til den i Eksempel 2.D benyttede, med et nyt bæremateriale 30 BP-2000 med et Hg-porevolumen på 4,01 1/kg og en BET-poreradium på 22,8 nm.A synthesis procedure similar to that used in Example 2.D was used, with a new carrier 30 BP-2000 having a Hg pore volume of 4.01 l / kg and a BET pore radius of 22.8 nm.
Bærematerialet blev før anvendelsen tørret i en ovn ved 150°C i 3 timer. Eksempel 2.D blev fulgt under anvendelse af 1,00 kg BP-2000 svarende til et totalt 35 porevolumen på 4,01 1. Den eneste forskel var, at mæng- 10 DK 173486 B1 den af kemiske komponenter blev opskaleret med en faktor 5,5 (4,01/0,728).Prior to use, the carrier was dried in an oven at 150 ° C for 3 hours. Example 2.D was followed using 1.00 kg BP-2000 corresponding to a total of 35 pore volume of 4.01 1. The only difference was that the amount of chemical components was scaled up by a factor of 5. , 5 (4.01 / 0.728).
Der opnåedes en syntesegel i bæreren med følgende sammensætning: 5 25 Si02 : 0,25 Al^ : 5,8 TPAOH : 9 NH3 : 220 H20 :A synthesis gel was obtained in the carrier of the following composition: SiO₂: 0.25 Al₂: 5.8 TPAOH: 9 NH3: 220H₂O:
100 EtOH100 EtOH
Der benyttedes samme procedurer som i Eksempel 2.c 10 ved tørring, imprægnering af siliciumoxidkilde, trinnet med hydrotermal autoklavering og vasketrinnet.The same procedures as in Example 2.c 10 were used for drying, impregnating the silica source, the hydrothermal autoclaving step and the washing step.
I Tabel 1 er anført størrelsen for krystaller fra synteseeksemplerne 2.A-2.D. Krystalstørrelser (L) er beregnet ud fra tilvækst i liniebredde ved XRPD ved 15 anvendelse af Scherrer-ligningen ved (501)- og (151)-reflektionerne, svarende til 20 ved henholdsvis 23,18° og 23,72°.Table 1 lists the size of crystals from Synthesis Examples 2.A-2.D. Crystal sizes (L) are calculated from line width increments at XRPD using the Scherrer equation at (501) and (151) reflections, corresponding to 20 at 23.18 ° and 23.72 °, respectively.
Tabel 1 20 & Prøve Lg01 (nm) I>151 (nm) _0__> 100____> 100_ _2.A.__36,5__77,7_ _2.B.__16,2__15,7_ 25 _2.B.*__37,4__25,B_ 2.C. 20,3 16,0 * _2.C.__38,7__76,9_ _2.D.__19,1__15,5_ _2.D.*__29,4_ 31,2_ _2.E._ 48,2 45,2Table 1 20 & Sample Lg01 (nm) I> 151 (nm) _0 __> 100 ____> 100_ _2.A .__ 36.5__77.7_ _2.B .__ 16.2__15.7_ 25 _2.B. * __ 37.4__25, B_ 2 .C. 20.3 16.0 * _2.C. 38.7__76.9_ _2.D .__ 19.1__15.5_ _2.D. * __ 29.4_ 31.2_ _2.E._ 48.2 45.2
Tabel 1 Beregnede krystalstcrrelser, L, ud fra Scherrer-ligningen ved henholdsvis 501- og 151-reflektioneme som angivet ved indices 501 og 151.Table 1 Calculated crystal sizes, L, from the Scherrer equation at the 501 and 151 reflections, respectively, as indicated by indices 501 and 151.
35 (*): Porøst bæremateriale fjernet ved pyrolyse (ref.(*): Porous support removed by pyrolysis (ref.
Eksempel 2).Example 2).
11 DK 173486 B111 DK 173486 B1
Derudover udførte man transmissions-elektronmikroskopi (TEM) (Philips EM430, 300 kV) på eksemplerne. Morfologien for partiklerne er en aggregation af små, ellipsoide partikler. Den ved XRPD bestemte størrelse 5 af eksemplerne bekræftes af TEM-biliederne, der viser partikler med en så lille krystalstørrelse som 8 nm.In addition, transmission electron microscopy (TEM) (Philips EM430, 300 kV) was performed on the examples. The morphology of the particles is an aggregation of small, ellipsoidal particles. The size 5 of the examples determined by XRPD is confirmed by the TEM images showing particles with a size as small as 8 nm.
BET overfladearealet for prøve B.l var 395,1 m /g med et ydre overfladeareal på 156,3 m /g. Zeolitten viste bemærkelsesværdige mesoporøse adsorptionsegenska-10 ber. Ud over det indre porevolumen for zeolitkrystallerne på 0,13 ml/g viste prøven porer med snæver størrelsesfordeling, en middelporeradius på 20 nm og et porevolumen på 0,54 ml/g.The BET surface area for sample B.l was 395.1 m / g with an outer surface area of 156.3 m / g. The zeolite showed remarkable mesoporous adsorption properties. In addition to the inner pore volume of the 0.13 ml / g zeolite crystals, the sample showed pores of narrow size distribution, a mean pore radius of 20 nm, and a pore volume of 0.54 ml / g.
15 Eksempel 3:Example 3:
Fjernelse af porøst bæremateriale ved pyrolyseRemoval of porous support by pyrolysis
Fjernelse af carbonbæreren blev opnået ved pyrolyse. Bæreren blev udspredt i et tyndt lag i en muf-felovn og opvarmet med en opvarmningshastighed på 20 2°C/minut fra 24eC til 250°C, ændret til l°C/minut fra 250°C til 400eC. Denne høje temperatur blev holdt i ca. seks timer i afhængighed af typen af carbonbæreren.Removal of the carbon support was achieved by pyrolysis. The support was spread in a thin layer in a muffle furnace and heated at a heating rate of 20 ° C / minute from 24 ° C to 250 ° C, changed to 1 ° C / minute from 250 ° C to 400 ° C. This high temperature was kept for approx. six hours depending on the type of carbon carrier.
Eksempel 4 $Example 4 $
25 Krystallisation af ZSM-5 i MgOCrystallization of ZSM-5 in MgO
Den porøse magnesiumoxidbærer blev fremstillet ved calcinering af magnesiumhydroxycarbonathydroxid, penta-hydrat (99% (MgC03)4, Mg(0H)2, 5H20, Aldrich) ved 700eC i 6 timer. BET-overfladearealet var 72 m2/g, den havde 30 en middelporeradius på 11,9 nm og et porevolumen på 0,36 ml/g.The porous magnesium oxide support was prepared by calcination of magnesium hydroxycarbonate hydroxide, pentahydrate (99% (MgCO 3) 4, Mg (OH) 2.5H 2 O, Aldrich) at 700 ° C for 6 hours. The BET surface area was 72 m 2 / g, it had a mean pore radius of 11.9 nm and a pore volume of 0.36 ml / g.
Syntesen af ZSM-5 med Si/Al = 50 blev udført som i Eksempel 2.D. Carbonsort (BP-700) var erstattet med 2,00 kg MgO (svarende til samme porevolumen som i 1,00 35 kg BP-700). Der benyttedes samme procedure og vægtede 12 DK 173486 B1 mængder af TEOS, TPAOH, Al(i-PrO)3, EtOH og NH3 som i Eksempel 2.D til syntesen af ZSM-5/MgO.The synthesis of ZSM-5 with Si / Al = 50 was performed as in Example 2.D. Carbon black (BP-700) was replaced by 2.00 kg MgO (corresponding to the same pore volume as in 1.00 35 kg BP-700). The same procedure was used and weighted amounts of TEOS, TPAOH, Al (i-PrO) 3, EtOH and NH3 as in Example 2.D for the synthesis of ZSM-5 / MgO.
XRPD udført på produktet viste tilstedeværelse af ZSM-5 med en krystalstørrelse på ca. 19,0 nm.XRPD performed on the product showed the presence of ZSM-5 with a crystal size of approx. 19.0 nm.
5 Eksempel 5:Example 5:
Fjernelse af porøs HgO bærer med syreRemoval of porous HgO carrier with acid
Den porøse MgO bærer blev fjernet fra det som i Eksempel 4 syntetiserede ZSM-5/MgO ved sur hydrolyse med 2 M HN03 ved 80°C i 2 timer.ZSM-5 blev frafiltre-10 ret, vasket med vand til pH-værdien for vaskevandet var 6-7 og tørret ved 110°C i 3 timer. XRPD udført på produktet viste ZSM-5 med en krystalstørrelse på 20,4 nm.The porous MgO support was removed from the ZSM-5 / MgO synthesized by acid hydrolysis with 2 M HNO 3 at 80 ° C for 2 hours, as filtered in Example 4. ZSM-5 was filtered off, washed with water to the pH the wash water was 6-7 and dried at 110 ° C for 3 hours. The XRPD performed on the product showed ZSM-5 with a crystal size of 20.4 nm.
Eksempel 6: 15 Krystallisation af LTA og SOD i siliciumoxid-aluminiumoxidExample 6: Crystallization of LTA and SOD in silica-alumina
Der udførtes en syntese i et begrænst område af sodalit (SOD) i jj-a1203 på følgende måde. Man imprægnerede 1 kg 5 vægt% Si02 i tj-A1203 (HTAS B-20, Haldor 20 Topsøe, A/S), der var calcineret ved 550°C, med 2,5 l af en 2 M NaOH opløsning. Aluminiumoxidet blev tørret ved 110°C i 2 timer og overført til et med PTFE foret bæger inden i en rustfri stål-autoklav indeholdende noget vand til undgåelse af en for stor fordampning fra 25 gelen. Autoklaven blev holdt opvarmet til 120°C i 18 timer. Produktet blev vasket grundigt med vand og tørret ved 110°C i 3 timer fulgt af calcinering ved 550°C i 6 timer.A synthesis in a limited range of sodalite (SOD) in jj-a1203 was performed as follows. 1 kg of 5 wt% SiO 2 was impregnated in tj-A1203 (HTAS B-20, Haldor 20 Topsoe, A / S) calcined at 550 ° C with 2.5 L of a 2 M NaOH solution. The alumina was dried at 110 ° C for 2 hours and transferred to a PTFE lined beaker inside a stainless steel autoclave containing some water to avoid excessive evaporation from the gel. The autoclave was kept heated to 120 ° C for 18 hours. The product was washed thoroughly with water and dried at 110 ° C for 3 hours followed by calcination at 550 ° C for 6 hours.
XRPD viste, at materialet kun indeholdt j?-A1203 og 30 sodalit. Krystal størrelsen for zeolitten blev ved hjælp af Scherrer-ligningen beregnet til at være 15,0 nm. Transmissions-elektronmikroskopi viste tilstedeværelse af aluminiumoxid og et krystallinsk materiale med visse krystaller, der var så små som 4 nm, hvilket er sammen- * 35 ligneligt med krystalstørrelsen for aluminiumoxidet.XRPD showed that the material contained only J-A1203 and 30 sodalite. The crystal size of the zeolite was calculated using the Scherrer equation to be 15.0 nm. Transmission electron microscopy showed the presence of alumina and a crystalline material with certain crystals as small as 4 nm, which is comparable to the crystal size of the alumina.
13 DK 173486 B113 DK 173486 B1
Linde type A (LTA) i i7-Al203 blev syntetiseret på tilsvarende måde. Man imprægnerede 1 kg 5 vægt% Si02 i η-Αΐ203 (HTAS B-20, Haldor Topsøe, A/S), der var calci-neret ved 550°C, med 2,5 1 af en 4 Μ KOH opløsning. Der 5 benyttedes samme procedurer i tørretrinnet, trinnet med hydrotermal autoklavering, vasketrinnet og calcineringen som ovenfor beskrevet.Linde type A (LTA) in i7-Al2O3 was similarly synthesized. 1 kg of 5 wt% SiO 2 was impregnated in η-Αΐ203 (HTAS B-20, Haldor Topsøe, A / S) calcined at 550 ° C with 2.5 L of a 4 4 KOH solution. The same procedures were used in the drying step, the hydrothermal autoclaving step, the washing step and the calcination as described above.
XRPD udført på produktet viste tilstedeværelse af T7-Al203 og zeolit. Zeolitten blev bestemt til at være 10 LTA med en ifølge Scherrer-ligningen beregnet krystalstørrelse på 18,3 nm.The XRPD performed on the product showed the presence of T7-Al2 O3 and zeolite. The zeolite was determined to be 10 LTA with a crystal size calculated at 18.3 nm according to the Scherrer equation.
Eksempel 7:Example 7:
Krystallisation af SOD i MgAl204 15 Som bæremateriale benyttedes magnesium-aluminium- spinel (MgAl204, på form af en katalysatorbærer calci-neret ved 750°C og med handelsnavnet "R67" som leveret af Haldor Topsøe A/S) med et porevolumen på 0,50 ml/g og en BET poreradius på 10,2 nm.Crystallization of SOD in MgAl2O4 As the carrier material, magnesium aluminum spinel (MgAl2O4, in the form of a catalyst support calcined at 750 ° C and with the trade name "R67" as supplied by Haldor Topsøe A / S) was used with a pore volume of 0, 50 ml / g and a BET pore radius of 10.2 nm.
20 Man neddyppede 1,00 kg MgAl204 i en opløsning af 1,00 kg TEOS og 0,86 kg EtOH (svarende til 50 vol%1.00 kg of MgAl2O4 was immersed in a solution of 1.00 kg of TEOS and 0.86 kg of EtOH (corresponding to 50 vol%
Et OH) i en time. Det imprægnerede MgAl204 blev tørret ved stuetemperatur, indtil ethanol var bortfordampet.One OH) for one hour. The impregnated MgAl2O4 was dried at room temperature until ethanol was evaporated.
Man opløste 3,20 kg NaOH (97%, Aldrich) og 0,95 kg 25 natriumaluminat (NaAl203, 54 vægt% Al203 og 41 vægt%3.20 kg NaOH (97%, Aldrich) and 0.95 kg sodium aluminate (NaAl 2 O 3, 54 wt% Al 2 O 3 and 41 wt% were dissolved)
Na20) i 1,00 kg vand. Det imprægnerede MgAl204 blev neddyppet i opløsningen i en time, tørret overfladisk med et håndklæde og ældet i to timer. Der opnåedes en syntesegel med følgende saammensætning: 30Na 2 O) in 1.00 kg of water. The impregnated MgAl2O4 was immersed in the solution for one hour, dried superficially with a towel and aged for two hours. A synthesis gel of the following composition was obtained: 30
Si02 s Al203 : 10,3 Na20 : 21,3 HjOSiO 2 s Al 2 O 3: 10.3 Na 2 O: 21.3 H 2 O
Derefter blev den overført til en porcelænsskål, anbragt i en rustfri stål-autoklav indeholdende noget 35 vand og autoklaveret hydrotermisk i 24 timer under sta- 14 DK 173486 B1 tiske betingelser.It was then transferred to a porcelain dish, placed in a stainless steel autoclave containing some 35 water and autoclaved hydrothermally for 24 hours under static conditions.
Produktet blev vasket med vand til pH-værdien for vaskevandet nåede 7-8, tørret ved 110°C i 3 timer og calcineret ved 550°c i 6 timer.The product was washed with water until the pH of the wash water reached 7-8, dried at 110 ° C for 3 hours and calcined at 550 ° C for 6 hours.
5 XRPD foretaget på produktet viste, at faserne var5 XRPD made on the product showed that the phases were
MgAl204 med spinelstruktur og zeolit med sodalitstruk-tur. Krystalstørrelsen for zeolitten blev ved hjælp af Scherrer-ligningen beregnet til at være 8,3 nm.MgAl2O4 with spinel structure and zeolite with sodalite structure. The crystal size of the zeolite, using the Scherrer equation, was calculated to be 8.3 nm.
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| Application Number | Priority Date | Filing Date | Title |
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| DK199801505A DK173486B1 (en) | 1998-11-18 | 1998-11-18 | Process for producing small, zeotypic crystals |
| DE69907853T DE69907853T2 (en) | 1998-11-18 | 1999-11-02 | Process for the production of small zeotype crystals |
| AT99121702T ATE240265T1 (en) | 1998-11-18 | 1999-11-02 | METHOD FOR PRODUCING SMALL ZEOTYPE CRYSTALS |
| DK99121702T DK1002764T3 (en) | 1998-11-18 | 1999-11-02 | Process for the preparation of small zeotype crystals |
| EP99121702A EP1002764B1 (en) | 1998-11-18 | 1999-11-02 | Method for preparation of small zeotype crytals |
| ES99121702T ES2198836T3 (en) | 1998-11-18 | 1999-11-02 | METHOD OF PREPARATION OF CRYSTALS ZEOTIPO OF SMALL SIZE. |
| US09/437,923 US6241960B1 (en) | 1998-11-18 | 1999-11-10 | Method for preparation of small zeotype crystals |
| JP32843699A JP4677069B2 (en) | 1998-11-18 | 1999-11-18 | Method for producing small zeotype crystals |
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| DK199801505A DK173486B1 (en) | 1998-11-18 | 1998-11-18 | Process for producing small, zeotypic crystals |
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| US6908604B2 (en) * | 1999-05-17 | 2005-06-21 | Exxonmobil Chemical Patents Inc. | Macrostructures of porous inorganic material and process for their preparation |
| SE512222C2 (en) * | 1998-06-29 | 2000-02-14 | Johan Sterte | Process for the preparation of macrostructures of microporous materials |
| ES2223372T3 (en) | 1999-12-06 | 2005-03-01 | Haldor Topsoe A/S | ZEOLITA MONOCRISTAL DEPREPARATION PROCEDURE. |
| US6620402B2 (en) * | 1999-12-06 | 2003-09-16 | Haldor Topsoe A.S | Method of preparing zeolite single crystals with straight mesopores |
| US6926882B2 (en) * | 2000-01-05 | 2005-08-09 | Exxonmobil Chemical Patents Inc. | Porous inorganic macrostructure materials and process for their preparation |
| CN1307099C (en) | 2000-12-28 | 2007-03-28 | 花王株式会社 | Fine zeolite particle |
| ATE389451T1 (en) | 2002-01-24 | 2008-04-15 | Haldor Topsoe As | METHOD FOR IMMOBILIZING A HOMOGENEOUS CATALYST, AND CATALYTIC MATERIAL |
| US6793911B2 (en) | 2002-02-05 | 2004-09-21 | Abb Lummus Global Inc. | Nanocrystalline inorganic based zeolite and method for making same |
| EP1430949B1 (en) * | 2002-12-10 | 2008-03-26 | Haldor Topsoe A/S | Process for catalytic dehydrogenation and catalyst therefore |
| WO2005098232A2 (en) * | 2004-03-26 | 2005-10-20 | Michigan State University | Method for the preparation of metal oxides in nanometric particle form |
| WO2011109601A1 (en) * | 2010-03-04 | 2011-09-09 | Shell Oil Company | Method of making sapo-34 membranes for use in gas separations |
| US8791040B2 (en) * | 2010-11-03 | 2014-07-29 | Fina Technology, Inc. | Catalysts containing nano-materials and methods of making and using same |
| US8852326B2 (en) * | 2011-03-07 | 2014-10-07 | Exxonmobil Research And Engineering Company | Aggregates of small particles of synthetic faujasite zeolite |
| WO2013145687A1 (en) * | 2012-03-26 | 2013-10-03 | 東ソー株式会社 | Mfi zeolite having uniform mesopores and method for producing same |
| CN111712592B (en) * | 2018-02-12 | 2024-04-26 | K·A·H·阿波-哈希马 | Method and device for producing alcohols from hydrocarbons |
| CN109513457B (en) * | 2018-11-22 | 2021-08-13 | 中国石油大学(华东) | Molecular sieve catalyst with modified magnesium aluminate spinel as carrier and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3329627A (en) * | 1963-04-19 | 1967-07-04 | Exxon Research Engineering Co | Synthetic zeolites |
| US3244643A (en) * | 1965-02-03 | 1966-04-05 | Socony Mobil Oil Co Inc | Method of preparing supported crystalline aluminosilicate composition |
| GB2118534B (en) * | 1982-04-15 | 1985-10-09 | South African Inventions | Electronically conductive tectosilicates |
| JPH0628706B2 (en) * | 1984-10-30 | 1994-04-20 | 宏志 鈴木 | Composite having zeolite, intercalation compound or crystal interstitial compound in pores of porous support and method for producing the same |
| US4567152A (en) * | 1984-12-13 | 1986-01-28 | Exxon Research And Engineering Co. | Co-matrixed zeolite and p/alumina |
| US4681864A (en) * | 1985-07-15 | 1987-07-21 | W. R. Grace & Co. | Cracking catalyst |
| GB8800045D0 (en) * | 1988-01-04 | 1988-02-10 | Exxon Chemical Patents Inc | Zeolite l |
| JPH01281106A (en) * | 1988-05-06 | 1989-11-13 | Akira Ishikawa | Production of inorganic permeation membrane |
| US4977122A (en) * | 1989-06-05 | 1990-12-11 | Exxon Research And Engineering Company | Cracking catalyst |
| JPH04200729A (en) * | 1990-11-30 | 1992-07-21 | Fujio Toda | Control of pore diameter of inorganic permeation film |
| JP3272119B2 (en) * | 1993-10-12 | 2002-04-08 | 中部電力株式会社 | Method for producing zeolite crystal membrane |
| JP3770504B2 (en) * | 1995-11-24 | 2006-04-26 | 株式会社ノリタケカンパニーリミテド | Zeolite membrane and method for producing the same |
| US6004527A (en) * | 1997-09-29 | 1999-12-21 | Abb Lummus Global Inc. | Method for making molecular sieves and novel molecular sieve compositions |
| JP2981884B1 (en) * | 1998-06-29 | 1999-11-22 | 工業技術院長 | Method for producing zeolite membrane |
-
1998
- 1998-11-18 DK DK199801505A patent/DK173486B1/en not_active IP Right Cessation
-
1999
- 1999-11-02 EP EP99121702A patent/EP1002764B1/en not_active Expired - Lifetime
- 1999-11-02 ES ES99121702T patent/ES2198836T3/en not_active Expired - Lifetime
- 1999-11-02 AT AT99121702T patent/ATE240265T1/en not_active IP Right Cessation
- 1999-11-02 DK DK99121702T patent/DK1002764T3/en active
- 1999-11-02 DE DE69907853T patent/DE69907853T2/en not_active Expired - Lifetime
- 1999-11-10 US US09/437,923 patent/US6241960B1/en not_active Expired - Lifetime
- 1999-11-18 JP JP32843699A patent/JP4677069B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69907853D1 (en) | 2003-06-18 |
| JP4677069B2 (en) | 2011-04-27 |
| JP2000154019A (en) | 2000-06-06 |
| DK1002764T3 (en) | 2003-09-01 |
| DK199801505A (en) | 2000-05-19 |
| ATE240265T1 (en) | 2003-05-15 |
| EP1002764B1 (en) | 2003-05-14 |
| US6241960B1 (en) | 2001-06-05 |
| ES2198836T3 (en) | 2004-02-01 |
| DE69907853T2 (en) | 2003-10-09 |
| EP1002764A1 (en) | 2000-05-24 |
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